CN108671923B - Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof - Google Patents

Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof Download PDF

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CN108671923B
CN108671923B CN201810440606.5A CN201810440606A CN108671923B CN 108671923 B CN108671923 B CN 108671923B CN 201810440606 A CN201810440606 A CN 201810440606A CN 108671923 B CN108671923 B CN 108671923B
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周倩倩
黎挺挺
郑岳青
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Ningbo University
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Abstract

The invention relates to a copper oxide/cobalt oxide core-shell catalyst for water electrolysis, comprising a copper foam base, CuOXCore, Co3O4A housing, wherein the CuOXIs CuO and Cu2A mixture of O. The invention also relates to a preparation method of the catalyst, which comprises the steps of synthesizing Cu (OH)2 NRs/CF electrode, synthetic Cu (OH)2@Co2CO3(OH)2NRs/CF electrode, synthetic CuOx@Co3O4NRs/CF electrodes. The invention has the beneficial effects that: (1) in-situ synthesis of multi-level CuO on a foamed copper substratex@Co3O4Nanorod array core-shell structure of CuOxIs a core of Co3O4The obtained electrode is a shell and shows excellent OER and HER activity and stability in alkaline electrolyte through the large electrochemical active surface area brought by the three-dimensional morphology of the shell and the synergistic effect among different metals; (2) the capability of catalyzing and electrolyzing water is high; (3) the raw material cost is low, and the preparation method is simple.

Description

Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof
Technical Field
The invention belongs to the technical field of electrocatalytic water decomposition, and particularly relates to a copper oxide/cobalt oxide core-shell structure catalyst for electrolyzing water, and a preparation method of the catalyst.
Background
Along with the rapid development of economy, the demand of energy sources in various fields in society is increasing, and meanwhile, the great use of traditional fossil fuels brings great harm to the living environment and health of human beings, so that the search for renewable clean energy sources capable of replacing the fossil fuels is a problem to be solved urgently at present.
Among clean energy sources, hydrogen energy is considered as the most ideal fossil fuel alternative energy source due to the advantages of high calorific value, water as the only combustion product and the like, and obtaining high-purity hydrogen by a method of electrochemically decomposing water is one of the most promising ways of obtaining renewable clean energy sources at present. The implementation of electrolytic water splitting involves two half-reactions: the oxygen evolution half-reaction (OER) at the anode and the hydrogen evolution half-reaction (HER) at the cathode require additional energy in the form of an overpotential (η) to overcome the various reaction energy barriers during the two half-reactions. The most efficient HER and OER electrocatalysts at present are Pt and RuO, respectively2(IrO2)。RuO2(IrO2) The material usually shows excellent OER electrocatalytic activity in an alkaline system, the stability of the material in an acidic system is greatly reduced, and the Pt material usually shows high-efficiency catalytic performance in the acidic system, but the catalytic activity of the Pt material in the alkaline environment is greatly reduced. In addition, Pt and RuO2(IrO2) Are all precious metal materials, and the expensive price and the rare reserves greatly prevent the large-scale commercial popularization of the materials in the electrolyzed water. Therefore, designing and developing a high-efficiency and stable non-noble metal bifunctional electrocatalyst in the same system to realize the full decomposition of water (having both OER and HER activities in the same basic or acidic system) has great application prospect and attraction.
In recent years, some catalysts of nano-sized heterostructures (heterostructures) exhibit excellent catalytic activity in electrocatalytic water decomposition. The heterogeneous catalytic material can generally combine the advantages of various materials, and can improve the electrochemical active surface area of the catalyst, expose more active sites, improve the conductivity of the material, and reduce the reaction activation energy. Meanwhile, transition metals such as Co, Ni, Fe, Mn and the like are also attracting attention as the application of the catalyst for electrolyzing water.
Copper metal, one of the members of transition metals, has the advantages of low cost, abundant reserves and the like, and is gradually applied to the field of electrocatalytic water decomposition in recent years, particularly applied to OER half reaction. At present, although metallic copper has made some progress in the electrocatalytic decomposition of water, its use in total decomposition of water (simultaneous oxygen and hydrogen evolution reactions) is still in the beginning. Therefore, the Cu-based heterostructure catalyst which is designed and synthesized and has efficient and stable OER and HER catalytic performances and can realize the full decomposition of water in the same electrolytic system has higher feasibility and practical application value.
The present application has been studied in this direction.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a copper oxide/cobalt oxide core-shell structured catalyst for use in the electrolysis of water, which comprises the following.
A copper oxide/cobalt oxide core-shell structured catalyst for electrolyzing water, the core-shell structured catalyst having a copper foam substrate, CuOXCore, Co3O4A housing, wherein the CuOXIs CuO and Cu2A mixture of O.
Preferably, CuOXThe core is a rod-like structure on a foamed copper substrate, the Co3O4The shell is CuOXA needle-like structure on the outer wall of the inner core.
Preferably, the CuOXThe diameter of the inner core is 190-210 nm; the Co3O4The length of the outer shell is 110-130nm, and the diameter is 45-55 nm.
Preferably, CuOXNeutral CuO and Cu2The molar ratio of O is 0.9-1.
The invention also aims to provide a preparation method of the copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis, which comprises the following steps: A. in a strong alkaline solution on an electrochemical workstation, taking foamy copper as a working electrode, taking a Pt electrode as a counter electrode, taking Ag/AgCl as a reference electrode, electrifying constant current for 30-50 min, and taking out the foamy copperWashing with distilled water, air drying to obtain surface covered with Cu (OH)2Nanorod Cu (OH)2NRs/CF electrodes; B. preparing an aqueous solution containing cobalt sulfate and urea, and adding Cu (OH) in the step A2The NRs/CF electrode is soaked in the water solution, and the whole is put into an oven to react for 3 to 5 hours, wherein the temperature of the oven is between 80 and 90 ℃; naturally cooling after reaction, taking out the electrode, cleaning and airing to obtain Cu (OH)2@Co2CO3(OH)2NRs/CF electrodes; C. reacting Cu (OH) in step B2@Co2CO3(OH)2Heating NRs/CF electrode at 390-410 deg.C for 3-5 hr, cooling to obtain CuOx@Co3O4NRs/CF electrode, which is copper oxide/cobalt oxide core-shell structure catalyst.
Preferably, in step A, the strong base solution is a 3M KOH solution.
Preferably, in step A, the constant current is 10 mA/cm2。
Preferably, in step B, the concentration of cobalt sulfate in the aqueous solution of cobalt sulfate and urea is 0.075M and the concentration of urea is 1.125M.
Compared with the prior art, the invention has the following beneficial effects: (1) in-situ synthesis of multi-level CuO on a foamed copper substratex@Co3O4Nanorod array core-shell structure of CuOxIs a core of Co3O4The obtained electrode is a shell and shows excellent OER and HER activity and stability in alkaline electrolyte through the large electrochemical active surface area brought by the three-dimensional morphology of the shell and the synergistic effect among different metals; (2) the capability of catalyzing and electrolyzing water is high; (3) the raw material cost is low, and the preparation method is simple.
Drawings
FIG. 1 is CuO in example 1x@Co3O4XRD result pattern of NRs/CF.
FIG. 2 shows Cu (OH) in example 12Scanning electron micrograph of NRs/CF.
FIG. 3 shows Cu (OH) in example 12@Co2CO3(OH)2 NRs/CFScanning electron microscopy of (a).
FIG. 4 is CuO in example 1x@Co3O4Scanning electron micrograph of NRs/CF.
FIG. 5 is CuO in example 1x@Co3O4Transmission electron microscopy of NRs/CF.
FIG. 6 is CuOx@Co3O4LSV curves comparing OER activity of NRs/CF.
FIG. 7 is CuOx@Co3O4Tafel slope comparison plot of OER activity for NRs/CF.
FIG. 8 is CuOx@Co3O4Electrochemical impedance contrast spectrum of OER activity of NRs/CF.
FIG. 9 is CuOx@Co3O4Stability testing of OER activity of NRs/CF is a comparative plot.
FIG. 10 is CuOx@Co3O4The current density of the OER activity of NRs/CF was 50 mA/cm2Comparative graph of stability test.
FIG. 11 is CuOx@Co3O4OER-active CuO for NRs/CFx@Co3O4CV curve of NRs/CF.
FIG. 12 is CuOx@Co3O4OER-active CuO for NRs/CFxCV curve of NRs/CF.
FIG. 13 is a graph of the electric double layer capacitance C of different electrodes obtained by calculation from the CV curves of FIGS. 11 and 12dlThe size of (2).
FIG. 14 is CuOx@Co3O4LSV curves of HER activity of NRs/CF are compared.
FIG. 15 is CuOx@Co3O4Tafel slope comparison plot of HER activity for NRs/CF.
FIG. 16 is CuOx@Co3O4Electrochemical impedance contrast spectra of HER activity for NRs/CF.
FIG. 17 is CuOx@Co3O4Comparative figure for stability testing of HER activity of NRs/CF.
Figure 18 is an SEM image of the product electrode after OER stability testing.
Figure 19 is an SEM image of the product electrode after HER stability testing.
FIG. 20 is a graph comparing electrochemical parameters between different catalytic electrodes.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a copper oxide/cobalt oxide core-shell structure catalyst for electrolyzing water, which is provided with a copper foam substrate (CF) and CuOXCore, Co3O4A housing, wherein the CuOXIs CuO and Cu2A mixture of O. Specifically, CuOXThe core is a rod-like structure on a foamed copper substrate, the Co3O4The shell is CuOXA needle-like structure on the outer wall of the inner core. The electrode catalyst in the invention is multi-level CuO synthesized in situ on a foam copper substratex@Co3O4Nanorod array core-shell structure catalyst (hereinafter referred to as CuO for short)x@Co3O4 NRs/CF）
Specifically, in the present invention, the CuO isXThe diameter of the inner core is 190-210nm, preferably 200 nm; the Co3O4The length of the shell is 110-130nm, the diameter is 45-55nm, preferably 120nm, and the diameter is 50 nm; CuO (copper oxide)XNeutral CuO and Cu2The molar ratio of O is 0.9 to 1, preferably 0.95.
The preparation method of the copper oxide/cobalt oxide core-shell structure catalyst comprises the following steps: A. in an electrochemical workstation, in a strong alkaline solution, taking foamy copper as a working electrode, taking a Pt electrode as a counter electrode and Ag/AgCl as a reference electrode, electrifying constant current for 30min-50 min, taking out foamy copper, cleaning with distilled water, and drying to obtain a product with the surface covered with Cu (OH)2Nanorod Cu (OH)2NRs/CF electrodes; B. preparing an aqueous solution containing cobalt sulfate and urea, and adding Cu (OH) in the step A2The NRs/CF electrode is immersed in the aqueous solution, and the whole is put into an oven to react for 3 hours to 5 hoursThe temperature of the oven is 80-90 ℃; naturally cooling after reaction, taking out the electrode, cleaning and airing to obtain Cu (OH)2@Co2CO3(OH)2NRs/CF electrodes; C. reacting Cu (OH) in step B2@Co2CO3(OH)2Heating NRs/CF electrode at 390-410 deg.C for 3-5 hr, cooling to obtain CuOx@Co3O4NRs/CF electrode, which is copper oxide/cobalt oxide core-shell structure catalyst.
Specific examples are as follows.
The first embodiment is as follows:
A. synthesis of Cu (OH)2 NRs/CF electrode: cu (OH)2The synthesis of NRs/CF is achieved by an anodization process in a three-electrode system. The method comprises the following specific steps: on an electrochemical workstation model CHI760E (Shanghai Chenghua), clean CF was used as a working electrode, a Pt electrode was used as a counter electrode, Ag/AgCl was used as a reference electrode, and a constant current of 10 mA/cm was applied in 3M KOH solution2Taking out CF after 40 min, washing the CF for a plurality of times by using distilled water, and naturally airing to obtain the blue Cu (OH) with uniformly covered surface2Nanorod Cu (OH)2NRs/CF electrodes.
B. Synthesis of Cu (OH)2@Co2CO3(OH)2NRs/CF electrode: cu (OH)2@Co2CO3(OH)2NRs/CF is obtained by a one-step low temperature hydrothermal reaction. First, 10 mL of an aqueous solution containing 0.075M cobalt sulfate and 1.125M urea was prepared and dissolved with stirring. Then adding Cu (OH) in the step A2 NRs/CF is soaked in a newly prepared pink transparent aqueous solution and reacts for 4 hours in an oven at the temperature of 85 ℃ with the temperature rise rate of 1 ℃ per minute. Taking out the electrode after the system is naturally cooled, washing the electrode for a plurality of times by distilled water and ethanol, and airing to obtain Cu (OH)2@Co2CO3(OH)2 NRs/CF。
C. Synthetic CuOx@Co3O4NRs/CF electrode: mixing Cu (OH)2@Co2CO3(OH)2NRs/CF is heated for 4 hours at 400 ℃ in an air atmosphere, the heating rate is 1 ℃ per minute, and CuO is obtained after coolingx@Co3O4NRs/CF electrodes. The electrode is the copper oxide/cobalt oxide core-shell structure catalyst.
Example two:
A. synthesis of Cu (OH)2 NRs/CF electrode: cu (OH)2The synthesis of NRs/CF is achieved by an anodization process in a three-electrode system. The method comprises the following specific steps: on an electrochemical workstation model CHI760E (Shanghai Chenghua), clean CF was used as a working electrode, a Pt electrode was used as a counter electrode, Ag/AgCl was used as a reference electrode, and a constant current of 10 mA/cm was applied in 3M KOH solution2Taking out CF after 30min, washing the CF for a plurality of times by using distilled water, and naturally airing to obtain the blue Cu (OH) with the surface uniformly covered2Nanorod Cu (OH)2NRs/CF electrodes.
B. Synthesis of Cu (OH)2@Co2CO3(OH)2NRs/CF electrode: cu (OH)2@Co2CO3(OH)2NRs/CF is obtained by a one-step low temperature hydrothermal reaction. First, 10 mL of an aqueous solution containing 0.075M cobalt sulfate and 1.125M urea was prepared and dissolved with stirring. Then adding Cu (OH) in the step A2 NRs/CF is soaked in a newly prepared pink transparent aqueous solution and reacts for 5 hours in an oven at 80 ℃ with the temperature rise rate of 1 ℃ per minute. Taking out the electrode after the system is naturally cooled, washing the electrode for a plurality of times by distilled water and ethanol, and airing to obtain Cu (OH)2@Co2CO3(OH)2 NRs/CF。
C. Synthetic CuOx@Co3O4NRs/CF electrode: mixing Cu (OH)2@Co2CO3(OH)2NRs/CF is heated for 3h under the condition of 410 ℃ in the air atmosphere, the heating rate is 1 ℃ per minute, and CuO is obtained after coolingx@Co3O4NRs/CF electrodes. The electrode is the copper oxide/cobalt oxide core-shell structure catalyst.
Example three:
A. synthesis of Cu (OH)2 NRs/CF electrode: cu (OH)2The synthesis of NRs/CF is achieved by an anodization process in a three-electrode system. The method comprises the following specific steps: on an electrochemical workstation model CHI760E (Shanghai Chenghua) at 3MIn KOH solution, cleaned CF is used as a working electrode, a Pt electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode, and constant current of 10 mA/cm is supplied2Taking out CF after 50 min, washing the CF for a plurality of times by using distilled water, and naturally airing to obtain the blue Cu (OH) with uniformly covered surface2Nanorod Cu (OH)2NRs/CF electrodes.
B. Synthesis of Cu (OH)2@Co2CO3(OH)2NRs/CF electrode: cu (OH)2@Co2CO3(OH)2NRs/CF is obtained by a one-step low temperature hydrothermal reaction. First, 10 mL of an aqueous solution containing 0.075M cobalt sulfate and 1.125M urea was prepared and dissolved with stirring. Then adding Cu (OH) in the step A2 NRs/CF is soaked in a newly prepared pink transparent aqueous solution and reacts for 3 hours in an oven at the temperature of 90 ℃, and the temperature rise rate is 1 ℃ per minute. Taking out the electrode after the system is naturally cooled, washing the electrode for a plurality of times by distilled water and ethanol, and airing to obtain Cu (OH)2@Co2CO3(OH)2 NRs/CF。
C. Synthetic CuOx@Co3O4NRs/CF electrode: mixing Cu (OH)2@Co2CO3(OH)2NRs/CF is heated for 5 hours at 390 ℃ in the air atmosphere, the heating rate is 1 ℃ per minute, and CuO is obtained after coolingx@Co3O4NRs/CF electrodes. The electrode is the copper oxide/cobalt oxide core-shell structure catalyst.
Comparative example:
in step B, blank CF was used instead of Cu (OH) under the same experimental conditions as in example one2Preparation of Co from NRs/CF2CO3(OH)2a/CF electrode. Then adding Cu (OH)2NRs/CF and Co2CO3(OH)2heating/CF under the same conditions to respectively obtain CuOxNRs/CF electrode and Co3O4a/CF electrode. Among them, CuOxNRs/CF electrode used as comparative example one, Co3O4the/CF electrode was used as comparative example II.
A series of tests were conducted on the catalyst electrode in example one of the present invention and the electrodes of comparative example one and comparative example twoTrial, wherein: all electrochemical tests were performed on the Shanghai Chenghua CHI760E electrochemical workstation in a three-electrode system with 1.0M KOH electrolyte. The effective area of the working electrode (example one electrode, comparative example two electrode) was 1 cm2The Pt sheet electrode is a counter electrode, and the Ag/AgCl electrode is a reference electrode. All voltages were converted to standard hydrogen electrodes (RHE) according to the nernst equation: eRHE=EAg/AgCl+0.0592 × pH + 0.197. For OER half reaction, the sweep rate of linear voltammetric scanning (LSV) is 5 mV/s, the sweep potential range is 1.0-2.0V vs RHE, and the voltage range of cyclic voltammetric scanning (CV) with different sweep rates (10-30 mV/s) is 0.10-0.20V vs Ag/AgCl in the non-faradaic region. Electrochemical Impedance Spectroscopy (EIS) recorded a voltage of 1.65V vs RHE. Chronopotentiometric (CP) voltage was 1.55V vs RHE (without iR compensation), and potentiometric electrolysis (CPE) was controlled at a current density of 50 mA/cm2Under the condition of the reaction. Unless otherwise noted, all OER electrochemical data were compensated by 80% iR. For the HER half-reaction, the sweep rate of the Linear voltammetric scan (LSV) was 5 mV/s, the sweep potential ranged from 0.2 to-0.6V vs RHE, the Electrochemical Impedance Spectroscopy (EIS) recorded a voltage of-0.2V vs RHE, and the Chronopotentiometry (CP) voltage was-0.3V vs RHE (no iR compensation). Unless otherwise noted, all OER data were 95% iR compensated and all HER data were 85% iR compensated.
In FIG. 1, CuOx@Co3O4XRD result of NRs/CF, surface CuOx@Co3O4NRs/CF made of CuO, Cu2O and Co3O4And (4) forming.
In FIG. 2, it can be seen that Cu (OH) is uniformly grown on the CF substrate2Nano array, in particular rod-like structure.
In FIG. 3, Cu (OH) can be seen2Uniformly growing a layer of Co on the nano array2CO3(OH)2Nano array of the Co2CO3(OH)2The nanoarrays are substantially needle-like structures attached to Cu (OH)2On the surface of the nanoarray.
In FIG. 4, the basic morphology after burning and Cu (OH) can be seen2@Co2CO3(OH)2The NRs/CF is kept consistent and the stability is good.
In FIG. 5, CuO can be seenx@Co3O4Is in a core-shell structure. In addition, the obtained electrode material is proved to be made of CuO, Cu by the characterization means of selective electron diffraction (SAED), EDX linear scanning, mapping, XPS and the like2O and Co3O4And (4) forming.
In FIG. 6, the catalytic material corresponding to the curve is sequentially CuO from left to rightx@Co3O4、Cu(OH)2@Co2CO3(OH)2、Co3O4、CuOx、CF、Cu(OH)2The base material is CF, and CuO can be seen in the figurex@Co3O4NRs/CF at Current densities of 50 and 100mA cm-2The over-positioning is only 240 mV and 259 mV, and the catalytic activity is far better than that of CuOxNRs/CF and other electrodes.
In FIG. 7, the catalytic material corresponding to the curve is CuO in the order from top to bottomx、Co3O4、Cu(OH)2@Co2CO3(OH)2、CuOx@Co3O4The base material was CF.
In FIG. 8, the catalytic materials corresponding to the curves are sequentially CuO from large radius to small radiusx、Cu(OH)2@Co2CO3(OH)2、Co3O4、CuOx@Co3O4The base material was CF.
In FIG. 9, the catalytic material corresponding to the upper line is CuOx@Co3O4The catalytic material corresponding to the lower line is CuOxThe base material was CF. FIG. 8 is a stability test at a corresponding voltage of 1.6V vs RHE, CuOx@Co3O4NRs/CF can maintain the current density at about 62 mA cm-2There was substantially no decrease in catalytic activity within 24 hours. And CuOxNRs/CF showed little catalytic activity.
In FIG. 10, the catalytic material corresponding to the lower line is CuOx@Co3O4The catalytic material corresponding to the upper line is CuOxThe base material was CF. FIG. 9 corresponds to a current density of 50 mA cm-2Stability test of (1): CuO (copper oxide)xThe stability of NRs/CF is rapidly reduced, and after a period of time, the catalyst falls off from the electrode surface, CuOx@Co3O4The NRs/CF stability did not change significantly, and the overpotential was kept at 245 mV.
As can be seen from a comparison of FIGS. 11 and 12, CuOx@Co3O4The electrochemical performance of NRs/CF is obviously better than that of CuOxNRs/CF. FIG. 13 shows the electric double layer capacitance C of different electrodes obtained by calculation of CV curvesdlSize of (1), from CdlCalculated to obtain CuOx@Co3O4The ECSA of the NRs/CF has an electrochemical active surface area of 5950 cm2，CuOx ECSA of NRs/CF was 275 cm2。CuOx@Co3O4NRs/CF 3 dimensional multilevel structure and CuOxAnd Co3O4The synergistic effect between the CuO and the CuOx@Co3O4The primary reason for the large electrochemically active surface area possessed by NRs/CF. The large ECSA is beneficial to exposing more active sites, promotes the permeation of electrolyte and can effectively increase the electrocatalytic activity.
Fig. 6 to 13 above show the results of the test of OER activity, and fig. 14 to 17 below show the results of the test of HER activity.
In FIG. 14, the catalytic materials corresponding to the curves are CF, Cu (OH) from left to right2、CuOx、Co3O4、Cu(OH)2@Co2CO3(OH)2、CuOx@Co3O4The base materials are all CF, and CuO can be seenx@Co3O4NRs/CF at Current densities of 50 and 100mA cm-2The over-positioning is only 242 mV and 265 mV, and the catalytic activity is far better than that of CuOxNRs/CF and other electrodes.
In FIG. 15, the catalytic material corresponding to the curve is CuO in the order from top to bottomx@Co3O4、Cu(OH)2@Co2CO3(OH)2、Co3O4、CuOxThe base material was CF.
In FIG. 16, the catalytic materials corresponding to the curves are sequentially CuO from large radius to small radiusx、Cu(OH)2@Co2CO3(OH)2、Co3O4、CuOx@Co3O4The base material was CF.
In FIG. 17, the catalytic material corresponding to the lower line is CuOx@Co3O4The catalytic material corresponding to the upper line is CuOxThe base material was CF. FIG. 17 is a stability test at a corresponding voltage of-0.3 vs RHE. CuO (copper oxide)x@Co3O4NRs/CF can maintain the current density at about 44 mA/cm2, and the catalytic activity is not substantially reduced within 24 hours.
Meanwhile, as can be seen from a comparison of fig. 18 and 19 and the electron micrograph before testing (fig. 4), the morphology after OER and HER stability was substantially consistent with that before electrolyzation, embodying CuOx@Co3O4NRs/CF good stability. Meanwhile, as can be seen from the comparison of the catalytic materials in fig. 20, the catalytic material of the present invention has good electrocatalytic performance.
In the invention, multi-level CuO is synthesized in situ on a Copper Foam (CF) substratex@Co3O4Nanorod array core-shell structure (CuO for short)x@Co3O4 NRs/CF，CuOxRepresents CuO and Cu2O mixture) of CuO, CuOxIs a core of Co3O4Is a shell. Due to the large electrochemical active surface area brought by the three-dimensional morphology of the electrode and the synergistic effect of different metals, the obtained electrode shows excellent OER and HER activity and stability in 1M KOH alkaline electrolyte. In the OER half-reaction, CuOx@Co3O4NRs/CF at current densities of 50 and 100mA/cm2The time-over-fix required only 240 and 259 mV, with a Tafel slope of 46 mV/s. In the HER half reaction, CuOx@Co3O4NRs/CF achieves 50 and 100mA/cm current density2The time-over-orientation only needs 242 and 265 mV, and the Tafel slope is 61 mV/s. CuO in stability testx@Co3O4NRs/CF can produce O for 24h2Or H2Without a decrease in catalytic performance, the faradaic efficiencies of OER and HER were 99.7% and 96.4%, respectively.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.

Claims (1)

1. The copper oxide/cobalt oxide core-shell structure catalyst for electrolyzing water is characterized by comprising a foamed copper substrate and CuOXCore, Co3O4A housing, wherein the CuOXIs CuO and Cu2A mixture of O;
CuOXthe inner core is a rod-shaped structure on the foam copper substrate; the CuOXThe diameter of the inner core is 190-210 nm; the Co3O4The length of the shell is 110-130nm, and the diameter is 45-55 nm; CuO (copper oxide)XNeutral CuO and Cu2The molar ratio of O is 0.9-1;
the core-shell structure catalyst is prepared by the following method:
A. in an electrochemical workstation, in a strong alkaline solution, taking foamy copper as a working electrode, taking a Pt electrode as a counter electrode and Ag/AgCl as a reference electrode, electrifying constant current for 30min-50 min, taking out foamy copper, cleaning with distilled water, and drying to obtain a product with the surface covered with Cu (OH)2Nanorod Cu (OH)2NRs/CF electrodes;
B. preparing an aqueous solution containing cobalt sulfate and urea, and adding Cu (OH) in the step A2The NRs/CF electrode is soaked in the water solution, and the whole is put into an oven to react for 3 to 5 hours, wherein the temperature of the oven is between 80 and 90 ℃; naturally cooling after reaction, taking out the electrode, cleaning and airing to obtain Cu (OH)2@Co2CO3(OH)2NRs/CF electrodes;
C. reacting Cu (OH) in step B2@Co2CO3(OH)2 Heating NRs/CF electrode at 390-410 deg.C for 3-5 hr, cooling to obtain CuOx @ Co3O4NRs/CF electrode, the electrode is copper oxide/cobalt oxide nucleocapsid structure catalyst;
in the step A, the strong base solution is 3M KOH solution; the constant current is 10 mA/cm2；
In the step B, the concentration of the cobalt sulfate in the aqueous solution of the cobalt sulfate and the urea is 0.075M, and the concentration of the urea is 1.125M.
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